CN112893062B - Corrosion-resistant treatment process for corrosion-resistant alloy pipe - Google Patents
Corrosion-resistant treatment process for corrosion-resistant alloy pipe Download PDFInfo
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Abstract
The invention discloses an anti-corrosion treatment process of an anti-corrosion alloy pipe, which comprises the following specific processing procedures: polishing the surface of the alloy pipe by adopting sand paper, sequentially carrying out ultrasonic treatment on the pipe by using an acetone solution and absolute ethyl alcohol for 5-6min respectively, soaking the pipe in a 1mol/L hydrochloric acid solution for 3-4min, washing the pipe by using deionized water, and drying the pipe for later use; adding the pipe into a surface treatment agent solution with the concentration of 15%, soaking for 5-6min at normal temperature, taking out and airing; and then spraying a layer of epoxy resin anticorrosive paint on the surface of the pipe. The surface treatment agent is used for pretreating the metal surface and then is compounded with a layer of coating, the surface treatment agent is of a hyperbranched structure, the end group of the surface treatment agent contains a large number of oxysilane, sulfhydryl and amino groups, the silicon hydroxyl generated by hydrolysis of the oxysilane bond can be combined with the hydroxyl on the surface of iron or aluminum metal in the metal, and copper can be bonded with the sulfhydryl groups, so that the combination capability can be improved.
Description
Technical Field
The invention belongs to the field of pipe processing, and relates to an anti-corrosion treatment process for an anti-corrosion alloy pipe.
Background
The metal pipe is easy to corrode in a moist external environment, so that a layer of anti-corrosion coating is usually compounded on the surface of the pipe, but the combination capability between the anti-corrosion coating and the metal pipe is weak, the stripping of the coating is easy to cause, the corrosion of the pipe is caused, and the silane coupling agent YRSiX is used in the prior art 3 Pretreatment is carried out on the metal surface, Y is an organic functional group combined with the coating, X is alkoxy, and Si (OH) is generated after hydrolysis 3 The silane coupling agent is easy to produce reverse adsorption, so that Y organic functional groups are adsorbed on the metal surface, and silanol groups are outwards, so that the Y functional groups cannot carry out crosslinking reaction with the coating, the coating is easy to peel off, and the corrosion resistance is reduced.
Disclosure of Invention
The invention aims to provide an anti-corrosion treatment process for an anti-corrosion alloy pipe, which comprises the steps of pretreating the metal surface through a surface treating agent, then compounding a layer of coating, wherein the surface treating agent is of a hyperbranched structure, the end group of the surface treating agent contains a large number of oxy silane, mercapto and amino groups, the silicon hydroxyl generated by hydrolysis of the oxy silane bond can be combined with the hydroxyl on the surface of iron or aluminum metal in the metal, metals without hydroxyl groups such as copper are not easy to treat by the oxy silane, but copper can be bonded with the mercapto, the simultaneous combination of various metals in the alloy is realized through introducing the oxy silane bond and the mercapto, the combination capability can be improved, and meanwhile, the surface treating agent is of a branched structure, so that the three-dimensional structure surface of the prepared polymer is uniformly compounded with a large number of the oxy silane bond and the mercapto, and the combination performance with the metal surface can be improved.
The aim of the invention can be achieved by the following technical scheme:
an anti-corrosion treatment process for anti-corrosion alloy pipes comprises the following specific processing procedures:
first, 400 is adopted # 、800 # 、1200 # 、1500 # Polishing the surface of the alloy pipe by sand paper, sequentially carrying out ultrasonic treatment on the pipe by using an acetone solution and absolute ethyl alcohol for 5-6min respectively, soaking the pipe in a 1mol/L hydrochloric acid solution for 3-4min, washing the pipe by deionized water, and drying the pipe for later use;
secondly, adding a surface treating agent into a mixed solvent to prepare a surface treating agent solution with the concentration of 15%, then adding the pipe into the surface treating agent solution, soaking for 5-6min at normal temperature, taking out and airing, so that a protective film is compounded on the surface of the pipe, a large amount of amino groups are uniformly grafted on the protective film, and the surface treating agent is a polymer with a terminal group containing sulfhydryl groups, oxo silane bonds, amino groups and branched structures; the mixed solvent is prepared by mixing ethanol and water according to the mass ratio of 7-8:1, the terminal group of the surface treating agent contains a large number of oxygen silane bonds, mercapto groups and amino groups, a large number of mercapto groups and oxygen silane bonds in the terminal group can react with metal, the bonding capacity of a protective film on the surface of the pipe and the pipe is improved, the content of the silane bonds capable of being polymerized and connected between adjacent polymer molecules is increased due to the hyperbranched three-dimensional polymer structure, the formed reticular structure is tightly connected to form a compact waterproof film, the metal surface has higher hydrophobic property due to the fact that the silane bonds are more, the metal surface is connected with metal through silicon hydroxyl groups due to the hyperbranched structure, a layer of siloxane bonds are formed outside due to the three-dimensional structure of the hyperbranched structure, namely, a large number of siloxane bonds are distributed at the joint of the film and the coating, the waterproof film forms a multi-layer structure, the waterproof anticorrosion performance is improved, the waterproof performance is prevented from being influenced by the fact that the waterproof film is directly added with silane bonds in the prior art, and the space oxygen silane is not reduced due to the fact that the hydrophobic property is not reduced;
thirdly, spraying a layer of epoxy resin anticorrosive paint on the surface of the pipe, so that a layer of protective film and a coating are sequentially compounded from inside to outside on the surface of the pipe after processing, and the prepared coating has very high adhesion performance and is not easy to peel and corrode due to the fact that a large amount of amino groups are arranged on the surface of the protective film and can react with epoxy groups in the epoxy resin anticorrosive paint, so that the coating and the protective film can be tightly combined, and meanwhile, the polymer in the protective film is in a hyperbranched structure, so that the amino groups on the surface of the protective film have a large amount of amino groups, the combination capability between the coating and the protective film is improved, and the combination performance between the protective film and the surface of the pipe is very high;
preferably, the surface treatment agent is prepared as follows:
(1) Adding bromoacetic acid into a reaction kettle, heating to 75-80 ℃, adding p-toluenesulfonic acid into the reaction kettle, slowly dropwise adding mercaptoethanol, controlling the dropwise adding within 30min, reacting at constant temperature for 4-4.5h, vacuumizing by a vacuum pump in the reaction process to remove generated water, accelerating the reaction, cooling to room temperature, washing with sodium bicarbonate aqueous solution, stirring and layering, and distilling an oil layer under reduced pressure to obtain bromomercaptoacetic acid ethyl ester; wherein mercaptoethanol and bromoacetic acid are added in a ratio of 1.2-1.5:1 by mass, and the addition of p-toluenesulfonic acid is 0.5% of the sum of the mass of bromoacetic acid and mercaptoethanol;
(2) Adding bromomercaptoacetic acid ethyl ester, 3-aminopropyl trimethoxysilane and 16% sodium bicarbonate solution into a reaction kettle simultaneously, reacting for 8-9h at 90-92 ℃, cooling, standing for layering, and carrying out reduced pressure distillation after separating a lower layer water layer to obtain silanized mercaptoacetic acid ethyl ester; the carbon atom ortho-position connected with bromine in the bromomercaptoacetic acid ethyl ester is connected with carbonyl, has higher activity and can carry out substitution reaction with amino; wherein bromothioglycollic acid ethyl ester and 3-aminopropyl trimethoxysilane are added according to the mass ratio of 1.4-1.7:1, and 20mL of 16% sodium bicarbonate solution is added into each gram of 3-aminopropyl trimethoxysilane;
(3) Adding paraformaldehyde and ethanol into a reaction kettle, adding silanized ethyl thioglycolate while stirring, cooling to 10-20 ℃, stirring for 30-40min, adding o-allylphenol, heating to 60-70 ℃ for reacting for 2h, refluxing for 7h, evaporating the solvent, standing the residual liquid, precipitating crystals, filtering, washing, and recrystallizing with ethanol to obtain a sulfhydryl silanized monomer; wherein the silylated ethyl thioglycolate and the o-allylphenol are added according to the mass ratio of 1:1.08-1.13, and simultaneously 43-44g of paraformaldehyde is added into each mole of silylated ethyl thioglycolate, and 100-120mL of ethanol is added;
(4) Adding ethyl acetate and an initiator into a reaction container, stirring and heating to 90-110 ℃, dissolving a sulfhydryl silanization monomer into the ethyl acetate to prepare a solution with the concentration of 30%, then simultaneously dropwise adding the sulfhydryl silanization monomer solution and triallylamine into the reaction container, controlling the dropwise addition within 2 hours, then carrying out heat preservation reflux reaction for 1-2 hours, adding the initiator into the reaction container, carrying out heat preservation reaction for 3-4 hours, then carrying out reduced pressure evaporation to remove a solvent, then adding epichlorohydrin and ethanol into the reaction container, stirring and mixing uniformly, heating to 80 ℃, slowly dropwise adding a 28% -30% sodium hydroxide solution within 1-1.5 hours, carrying out reaction for 1.5-2 hours at the temperature of 95-105 ℃, then carrying out reduced pressure evaporation to remove the solvent, washing with water to be neutral, and then carrying out drying to obtain the epoxy hyperbranched polymer; wherein the mass ratio of the mercapto-silanized monomer to the triallylamine is 10:1.2-1.3, the addition amount of the ethyl acetate is 1.1-1.3 times of the total mass of the mercapto-silanized monomer and the triallylamine, the addition amount of the initiator is 0.2% -0.4% of the total mass of the mercapto-silanized monomer and the triallylamine, and the addition amount of the initiator for the second time is one fourth of the first time; the initiator is one of azodiisobutyronitrile and di-tert-butyl peroxide; the addition amount of the epichlorohydrin is 18-19% of the sum of the mass of the mercapto-silylated monomer and the mass of the triallylamine, and the addition amount of the sodium hydroxide is 3.4-3.6% of the sum of the mass of the mercapto-silylated monomer and the mass of the triallylamine; the addition amount of the sulfhydryl silanization monomer and the triallylamine is controlled, so that the prepared hyperbranched polymer is blocked by the sulfhydryl silanization monomer, and further, the prepared hyperbranched polymer terminal group contains a large amount of oxysilane bonds and sulfhydryl groups;
(5) Adding the epoxidized hyperbranched polymer, the concentrated ammonia water and the ethanol into a reaction kettle at the same time, stirring and reacting for 30-40min at normal temperature, and then decompressing and steaming to remove the solvent and unreacted micromolecular substances to obtain a surface treating agent; because a large number of epoxy groups are introduced into the epoxidized hyperbranched polymer, the epoxy groups can react with amino groups, so that a large number of amino groups are introduced into the prepared surface treatment agent; the prepared surface treating agent is of a hyperbranched structure, the end group of the surface treating agent contains a large amount of oxysilane, mercapto and amino, the silicon hydroxyl generated by hydrolysis of the oxysilane bond can be combined with the hydroxyl on the surface of iron or aluminum metal in the metal, the metal without hydroxyl groups such as copper is not easy to treat with the oxysilane, but copper can be bonded with the mercapto, the simultaneous combination of various metals in the alloy can be realized by simultaneously introducing the oxysilane bond and the mercapto, the combination capacity can be improved, and meanwhile, the surface treating agent is of a branched structure, so that the surface of the prepared polymer three-dimensional structure is uniformly compounded with a large amount of oxysilane bond and mercapto, the combination performance with the surface of the metal can be improved, and the direct use of a silane coupling agent YRSiX in the prior art is effectively avoided 3 Y is an organic functional group bonded to the coating, and X is Si (OH) generated after hydrolysis of the alkoxy group 3 The silane coupling agent is easy to produce reverse adsorption, so that Y organic functional groups are adsorbed on the metal surface, and silanol groups are outwards, so that the Y functional groups cannot carry out crosslinking reaction with the coating, the coating is easy to peel off, and the corrosion resistance is reduced; whether the amino group in the hyperbranched surface treating agent reacts with the metal surface or not, the three-dimensional structure of the hyperbranched surface treating agent determines the functional group ammonia which can react with the coating on the surface after the metal surface treatmentThe base is not reduced, and the phenomenon of reverse adsorption is not caused.
The invention has the beneficial effects that:
the metal is firstly treated by the surface treating agent, so that a layer of waterproof film is formed on the surface of the metal, wherein the surface treating agent contains a large amount of oxysilane and contains a large amount of mercapto groups, the silicon hydroxy groups generated by hydrolysis of the oxysilane bonds can be combined with the hydroxy groups on the surface of iron or aluminum metal in the metal, the metal without hydroxy groups such as copper is not easy to treat by the oxysilane, but the copper can be bonded with the mercapto groups, and the simultaneous combination of a plurality of metals in the alloy can be realized by introducing the oxysilane bonds and the mercapto groups simultaneously, so that the combination capability can be improved, and the problem of lower combination capability caused by the combination of the oxysilane groups and the metal only is effectively solved.
The surface treating agent is a hyperbranched structure, a large amount of oxysilane, mercapto and amino are introduced into the end group of the surface treating agent, the silicon hydroxyl generated by hydrolysis of the oxysilane bond can be combined with the hydroxyl on the surface of iron or aluminum metal in metal, the amino can be combined with the coating, the surface treating agent can be firmly combined with the surface of metal and the coating, the adhesive force with the coating is improved, the hyperbranched structure of the three-dimensional structure enables the surface treating agent to be combined with the surface of metal, the amino, the oxysilane and the mercapto are formed on the composite layer of the surface treating agent and the surface of metal, and simultaneously, a large amount of amino, mercapto and oxysilane bonds are formed on the joint of the outer layer and the coating, the coating and the surface of metal can react with the surface treating agent, so that the silane coupling agent YRSiX in the prior art is effectively avoided 3 Y is an organic functional group bonded to the coating, and X is Si (OH) generated after hydrolysis of the alkoxy group 3 The silane coupling agent is easy to produce reverse adsorption, so that Y organic functional groups are adsorbed on the metal surface, and silanol groups are outwards, so that the Y functional groups cannot carry out crosslinking reaction with the coating, the coating is easy to peel off, and the corrosion resistance is reduced; whether the amino group in the hyperbranched surface treating agent reacts with the metal surface or not, the three-dimensional structure of the hyperbranched surface treating agent determines that the amino group of the functional group of the surface capable of reacting with the coating after the metal surface treatment is not reduced, and further the phenomenon of reverse adsorption is not caused.
The surface treating agent is of a hyperbranched structure, the end group of the surface treating agent contains a large number of oxy silane bonds, mercapto groups and amino groups, the content of the silane bonds capable of being polymerized and connected between adjacent polymer molecules is increased due to the hyperbranched three-dimensional polymer structure, so that the formed reticular structure is tightly connected to form a compact waterproof film, the metal surface has higher hydrophobic property due to the large content of the silane bonds, the metal surface and the metal connection part are connected through silicon hydroxyl groups to form the silane bond waterproof film due to the hyperbranched structure, the outer layer of the waterproof film also has a layer of siloxane bonds due to the three-dimensional structure of the hyperbranched structure, namely, the connection part of the waterproof film and the coating is also distributed with a large number of siloxane bonds, so that the waterproof film forms a multi-layer waterproof structure, the waterproof anti-corrosion performance is improved, the phenomenon that when the silane coupling agent is directly added in the prior art, the part of the oxy silane cannot be crosslinked due to the steric hindrance effect is avoided, the hydrophobic performance is reduced, and the anti-corrosion performance is reduced.
Detailed Description
The present invention is described in further detail below with reference to examples, but is not limited thereto.
The raw materials used in the following examples are all industrial products and are commercially available;
the aluminum-copper alloy pipe is subjected to corrosion prevention treatment, and the specific treatment process is as follows:
example 1:
an anti-corrosion treatment process for anti-corrosion alloy pipes comprises the following specific processing procedures:
first, 400 is adopted # 、800 # 、1200 # 、1500 # Polishing the surface of the alloy pipe by sand paper, sequentially carrying out ultrasonic treatment on the pipe by using an acetone solution and absolute ethyl alcohol for 5-6min respectively, soaking the pipe in a 1mol/L hydrochloric acid solution for 3min, washing the pipe by deionized water, and drying the pipe for later use;
secondly, adding the surface treating agent A into a mixed solvent to prepare a surface treating agent solution with the concentration of 15%, then adding the pipe into the surface treating agent solution, soaking for 5-6min at normal temperature, taking out and airing, wherein the mixed solvent is prepared by mixing ethanol and water according to the mass ratio of 8:1;
thirdly, spraying a layer of epoxy resin anticorrosive paint on the surface of the pipe, so that a layer of protective film and a layer of coating are sequentially compounded on the surface of the processed pipe from inside to outside.
Example 2:
the specific preparation process of the epoxy resin anticorrosive paint used in example 1 is as follows:
adding 32g of epoxy resin, 24mL of n-butanol and 5mL of dimethylbenzene into a stirring kettle simultaneously, stirring and mixing to obtain an epoxy resin solution, then adding 18g of zinc powder, 6g of titanium dioxide, 6g of talcum powder, 10mL of ethylene glycol diethyl ether acetate and 0.8g of defoamer into the epoxy resin solution, stirring and mixing uniformly at a high speed to obtain a component A, then mixing uniformly 15g of polyamide curing agent, 6g of n-butanol, 8g of dimethylbenzene and 15g of ethanol to obtain a component B, and then mixing uniformly the component B and the component A to obtain the epoxy resin anticorrosive paint.
Comparative example:
the surface treating agent A used in example 1 was replaced with one of the surface treating agent B, the surface treating agent C, the surface treating agent D or 3-aminopropyl trimethoxysilane, wherein the specific preparation process of the surface treating agent A, the surface treating agent B, the surface treating agent C and the surface treating agent D is described in detail as follows:
(1) The preparation process of the surface treating agent A is as follows:
step 1, adding 13.9g of bromoacetic acid into a reaction kettle, heating to 80 ℃, adding 0.12g of p-toluenesulfonic acid into the reaction kettle, slowly dropwise adding 10.1g of mercaptoethanol, controlling dropwise adding within 30min, reacting at constant temperature for 4.5h, vacuumizing by a vacuum pump in the reaction process to remove generated water, cooling to room temperature, washing with sodium bicarbonate aqueous solution, stirring, layering, and distilling an oil layer under reduced pressure to obtain bromomercaptoacetic acid ethyl ester; infrared analysis of the product revealed that the product was found to be at 2526cm -1 Has an absorption peak of-SH at 1734cm -1 An absorption peak with an ester group;
step 2, adding 15g of bromomercaptoacetic acid ethyl ester, 8.95g of 3-aminopropyl trimethoxysilane and 179mL of sodium bicarbonate solution with mass concentration of 16% into a reaction kettle simultaneously, reacting for 8h at 92 ℃, cooling, standing, layering, separatingRemoving a lower water layer, and then performing reduced pressure distillation to obtain silanized ethyl thioglycolate; infrared analysis of the product, 1085cm -1 An absorption peak of 3281cm at which Si-O bond appears -1 an-NH-infrared absorption peak appears at the position;
step 3, adding 2.17g of paraformaldehyde and 20mL of ethanol into a reaction kettle, adding 14.9g of silanized ethyl thioglycolate while stirring, cooling to 15 ℃, stirring for 30min, adding 7.34g of o-allylphenol into the reaction kettle, heating to 70 ℃ for 2h, reacting for 7h, refluxing, standing residual liquid after removing solvent by distillation, precipitating crystals, filtering, washing, and recrystallizing with ethanol to obtain a sulfhydryl silanized monomer; infrared analysis of the product showed 1087cm -1 An absorption peak of 1257cm at which Si-O bond appears -1 The absorption peak of C-O bond in phenolic hydroxyl appears at 1638cm -1 An absorption peak of c=c appears at;
step 4, adding ethyl acetate and 0.051g of an initiator into a reaction container, stirring and heating to 90-110 ℃, dissolving 20g of a mercapto silane monomer into ethyl acetate to prepare a solution with the mass concentration of 30%, then simultaneously dropwise adding the mercapto silane monomer solution and 2.5g of triallylamine into the reaction container, controlling the dropwise adding within 2 hours, then carrying out heat preservation and reflux reaction for 2 hours, adding 0.017g of the initiator into the reaction container, carrying out heat preservation and reaction for 4 hours, then carrying out reduced pressure evaporation to remove the solvent, then adding 4.16g of epichlorohydrin and 30mL of ethanol into the reaction container, stirring and mixing uniformly, heating to 80 ℃, slowly dropwise adding 6.53g of a sodium hydroxide solution with the mass concentration of 30% within 1.5 hours, carrying out reaction for 2 hours at the temperature of 100 ℃, then carrying out reduced pressure evaporation to remove the solvent, washing with water to neutrality, and then carrying out drying to obtain the epoxy hyperbranched polymer; the infrared analysis of the product revealed 914cm -1 An infrared absorption peak of the epoxy group appears at the site; three alkylene groups in triallylamine are positioned in three different directions and can react with a sulfhydryl silanization monomer in three different directions to form a hyperbranched structure;
step 5, adding 20g of an epoxidized hyperbranched polymer, 2.5mL of concentrated ammonia water and 20mL of ethanol into a reaction kettle simultaneously, stirring at normal temperature for reaction for 40min, and then decompressing and evaporating to remove a solvent and unreacted micromolecular substances to obtain a surface treating agent A; infrared analysis of the product showed thatAt 3286 and 3378cm -1 The amino group has a stretching vibration peak at 876cm -1 The position is provided with a deformation vibration peak of an amino group;
(2) The preparation process of the surface treating agent B comprises the following steps:
step 1, adding 2.17g of paraformaldehyde and 20mL of ethanol into a reaction kettle, adding 8.95g of 3-aminopropyl trimethoxysilane while stirring, cooling to 15 ℃, stirring for 30min, adding 6.7g of o-allylphenol into the reaction kettle, heating to 70 ℃, reacting for 2h, refluxing for 7h, evaporating the solvent, standing the residual liquid, precipitating crystals, filtering, washing, and recrystallizing with ethanol to obtain a silanized monomer; infrared analysis of the product showed 1083cm -1 An absorption peak of 1256cm at which Si-O bond appears -1 An absorption peak of C-O bond in phenolic hydroxyl group appears at the position;
step 2, adding ethyl acetate and 0.051g of an initiator into a reaction container, stirring and heating to 90-110 ℃, dissolving 15.6g of a silanized monomer into ethyl acetate to prepare a solution with the mass concentration of 30%, then simultaneously dropwise adding a silanized monomer solution and 2.5g of triallylamine into the reaction container, controlling the dropwise adding within 2 hours, then carrying out heat preservation and reflux reaction for 2 hours, adding 0.017g of the initiator into the reaction container, carrying out heat preservation and reaction for 4 hours, then carrying out reduced pressure evaporation to remove the solvent, then adding 4.16g of epichlorohydrin and 30mL of ethanol into the reaction container, stirring and mixing uniformly, heating to 80 ℃, slowly dropwise adding 6.53g of a sodium hydroxide solution with the mass concentration of 30% within 1.5 hours, carrying out reaction for 2 hours at the temperature of 100 ℃, then carrying out reduced pressure evaporation to remove the solvent, washing with water to neutrality, and then carrying out drying to obtain the epoxidized hyperbranched polymer; infrared analysis of the product revealed 917cm -1 An infrared absorption peak of the epoxy group appears at the site;
step 3, adding 20g of an epoxidized hyperbranched polymer, 2.5mL of concentrated ammonia water and 20mL of ethanol into a reaction kettle simultaneously, stirring at normal temperature for reaction for 40min, and then evaporating under reduced pressure to remove a solvent and unreacted micromolecular substances to obtain a surface treating agent B; infrared analysis of the product revealed that the product was observed at 872cm -1 There is a deformation vibration peak of amino.
(3) The preparation process of the surface treating agent C comprises the following steps:
step 1, 20g of the surface treatment agent A is preparedThe sulfhydryl silanization monomer prepared in the process is evenly mixed with 5.9g of epichlorohydrin and 30mL of ethanol, then heated to 80 ℃, 6.53g of sodium hydroxide solution with mass concentration of 30% is slowly added dropwise in 1.5h, the temperature is raised to 100 ℃ for 2h, then the solvent is distilled off under reduced pressure, then the mixture is washed to be neutral by water, and then the mixture is dried, so that the epoxidized sulfhydryl silanization monomer is obtained; the infrared analysis of the product revealed that 915cm -1 An infrared absorption peak of the epoxy group appears at the site;
step 2, adding 20g of epoxidized mercapto silanization monomer, 3mL of strong ammonia water and 26mL of ethanol into a reaction kettle simultaneously, stirring at normal temperature for reaction for 40min, and then decompressing and evaporating solvent and unreacted micromolecular substances to obtain a surface treating agent C; infrared analysis of the product revealed that at 3283 and 3376cm -1 There is an amino stretching vibration peak.
(4) The preparation process of the surface treating agent D is the same as that of the surface treating agent A, wherein triallylamine in the step 4 is replaced by 1, 5-hexadiene, and the hydrosulfide-based silane monomer has large steric hindrance due to the steric hindrance effect and forms a chain structure in the polymerization process with the 1, 5-hexadiene.
Test example:
1. taking an aluminum-copper alloy test piece plate material of the same material as a pipe according to the GB/T5210-2006 standard, treating the surface of the test piece plate material according to the method in the embodiment 1, enabling a layer of protective film and a layer of coating to be sequentially attached to the surface of the test piece plate material, bonding a test column to the surface of the coating by using an adhesive, and after the adhesive is cured, combining the test to a tensile testing machine to measure the adhesive force of the coating, wherein the measurement result is as follows: the adhesive force of the surface treating agent A to the coating after the test piece treatment is 10.13MPa, the adhesive force of the surface treating agent A to the coating after the test piece treatment is 9.54MPa, the adhesive force of the surface treating agent A to the coating after the test piece treatment is 7.61MPa, the adhesive force of the surface treating agent A to the coating after the test piece treatment is 8.72MPa, and the adhesive force of the surface treating agent A to the coating after the test piece treatment is 7.26MPa; it is known that after the surface treatment agent A is treated, a layer of coating is sprayed, the coating has higher adhesive force, and the surface treatment agent A is in a hyperbranched structure, because the end group of the surface treatment agent A contains a large amount of oxysilane, mercapto and amino, the silicon hydroxyl generated by hydrolysis of the oxysilane bond can be combined with the hydroxyl of the surface of aluminum metal in the metal, the metal without hydroxyl groups such as copper is not easy to treat with the oxysilane, but copper can be bonded with the mercapto, the simultaneous combination of various metals in the alloy is realized by introducing the oxysilane bond and the mercapto, the bonding capability can be improved, and meanwhile, because the surface treatment agent is in a branched structure, the three-dimensional structure surface of the prepared polymer is uniformly compounded with a large amount of oxysilane bond and mercapto, the bonding capability with the surface of the metal is improved, and the amino content in the end group of the hyperbranched structure is higher, further, the action sites between the coating and the epoxy resin coating are increased, the acting force between the coating and the protective film is improved, and because the three-dimensional polymer structure of hyperbranched polymer can increase the content of the silane bond between adjacent polymer molecules, the adhesive bond between the adjacent polymer molecules can be increased, the adhesive force between the surface of the surface is reduced, the adhesive force between the surface of the surface is not reduced, the surface of the surface is easy to form a film with the adhesive force between the surface of the metal, the surface is reduced, the adhesive force is reduced, the surface of the surface is not is easy to be adsorbed with the surface of the metal, and the adhesive force is reduced, and the surface of the surface is not has the adhesive force with the adhesive bond between the surface layer is formed, the adhesive force is reduced, and when the 3-aminopropyl trimethoxysilane is directly used for treatment, the reverse adsorption is possible, and simultaneously, mercapto which acts with copper is not introduced, so that the acting sites are reduced, and the adhesive force is reduced; the surface treating agent D has a chain structure due to the steric hindrance effect, silanol groups and sulfhydryl groups in chain parts of chain molecules of the chain structure can face outwards, and sites formed by silanol polymerization into a network structure among the chain molecules are reduced, so that the adhesion performance of the surface treating agent D is reduced.
2. Taking an aluminum copper alloy test piece plate material of the same material as a pipe, treating the surface of the test piece plate material according to the method in the embodiment 1, so that a layer of protective film and a layer of coating are sequentially attached to the surface of the plate material, wherein the protective film layer is respectively treated by a surface treating agent A, a surface treating agent B, a surface treating agent C, a surface treating agent D and 3-aminopropyl trimethoxysilane to obtain the protective film layer, when the test piece plate material treated by five different treating agents is treated in a neutral salt spray box according to the GB/T1771-2007 standard, observing the surface morphology of the test piece, the surfaces of the test piece treated by the surface treating agent A and the surface treating agent B are free from rust, the surfaces of the test piece treated by the surface treating agent C and the 3-aminopropyl trimethoxysilane are provided with a large number of rust spots, and the surface of the test piece treated by the surface treating agent D is provided with rust spots; the surface treating agent A and the surface treating agent B are hyperbranched structures, the end groups of the surface treating agent contain a large amount of oxygen-based silane bonds, the content of silane bonds capable of being polymerized and connected between adjacent polymer molecules is increased due to the hyperbranched three-dimensional polymer structure, the formed reticular structure is tightly connected, the metal surface has higher hydrophobic property due to the large content of silane bonds, the metal surface and the metal connection part are connected through silicon hydroxyl groups to form a silane bond waterproof film due to the hyperbranched structure, the outer layer of the waterproof film also has a layer of siloxane bonds due to the three-dimensional structure of the hyperbranched structure, the waterproof film forms a multi-layer waterproof structure, the waterproof and anti-corrosion performance is improved, the hyperbranched property is further improved, the content of silicon hydroxyl groups which are polymerized with each other is reduced due to the steric hindrance effect of the surface treating agent C and the 3-aminopropyl trimethoxysilane is reduced, the waterproof structure is reduced, the silane bond content distributed on the outer side is reduced, and the hydrophobic property of the waterproof structure is reduced.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (6)
1. The corrosion-resistant treatment process for the corrosion-resistant alloy pipe is characterized by comprising the following specific processing steps of:
firstly, polishing the surface of an alloy pipe by adopting sand paper, sequentially carrying out ultrasonic treatment on the pipe by using an acetone solution and absolute ethyl alcohol for 5-6min respectively, soaking the pipe in a 1mol/L hydrochloric acid solution for 3-4min, and then washing the pipe by using deionized water for drying for later use;
secondly, adding a surface treating agent into a mixed solvent to prepare a surface treating agent solution with the concentration of 15%, then adding the pipe into the surface treating agent solution, soaking for 5-6min at normal temperature, taking out and airing, wherein the surface treating agent is a polymer with an end group containing an oxo silane bond, a mercapto group and an amino group;
thirdly, spraying a layer of epoxy resin anticorrosive paint on the surface of the pipe;
wherein the preparation process of the surface treating agent comprises the following steps:
(1) Adding bromoacetic acid into a reaction kettle, heating to 75-80 ℃, adding p-toluenesulfonic acid into the reaction kettle, slowly dripping mercaptoethanol into the reaction kettle, reacting for 4-4.5 hours at constant temperature, cooling to room temperature, washing with sodium bicarbonate aqueous solution, stirring and layering, and carrying out reduced pressure distillation on an oil layer to obtain bromomercaptoacetic acid ethyl ester;
(2) Adding bromomercaptoacetic acid ethyl ester, 3-aminopropyl trimethoxysilane and 16% sodium bicarbonate solution into a reaction kettle simultaneously, reacting for 8-9h at 90-92 ℃, cooling, standing for layering, and carrying out reduced pressure distillation after separating a lower layer water layer to obtain silanized mercaptoacetic acid ethyl ester;
(3) Adding paraformaldehyde and ethanol into a reaction kettle, adding silanized ethyl thioglycolate while stirring, cooling to 10-20 ℃, stirring for 30-40min, adding o-allylphenol, heating to 60-70 ℃ for reacting for 2h, refluxing for 7h, evaporating the solvent, standing the residual liquid, precipitating crystals, filtering, washing, and recrystallizing with ethanol to obtain a sulfhydryl silanized monomer;
(4) Adding ethyl acetate and an initiator into a reaction container, stirring and heating to 90-110 ℃, dissolving a sulfhydryl silanization monomer into the ethyl acetate to prepare a solution with the concentration of 30%, then simultaneously dropwise adding the sulfhydryl silanization monomer solution and triallylamine into the reaction container, controlling the dropwise addition within 2 hours, then carrying out heat preservation reflux reaction for 1-2 hours, adding the initiator into the reaction container, carrying out heat preservation reaction for 3-4 hours, then carrying out reduced pressure evaporation to remove a solvent, then adding epichlorohydrin and ethanol into the reaction container, stirring and mixing uniformly, heating to 80 ℃, slowly dropwise adding 28-30% sodium hydroxide solution, heating to 95-105 ℃ to react for 1.5-2 hours, then carrying out reduced pressure evaporation to remove the solvent, washing with water to be neutral, and then drying to obtain the epoxidized hyperbranched polymer;
(5) And (3) adding the epoxidized hyperbranched polymer, the concentrated ammonia water and the ethanol into a reaction kettle at the same time, stirring and reacting for 30-40min at normal temperature, and then decompressing and steaming to remove the solvent and unreacted micromolecular substances to obtain the surface treating agent.
2. The corrosion-resistant treatment process for corrosion-resistant alloy pipes according to claim 1, wherein the mixed solvent in the second step is prepared by mixing ethanol and water in a mass ratio of 7-8:1.
3. The corrosion-resistant treatment process for corrosion-resistant alloy pipes according to claim 1, wherein mercaptoethanol and bromoacetic acid are added in the ratio of 1.2-1.5:1 in terms of the mass ratio, and p-toluenesulfonic acid is added in an amount of 0.5% of the sum of the mass amounts of bromoacetic acid and mercaptoethanol.
4. The corrosion-resistant treatment process of the corrosion-resistant alloy pipe according to claim 1, wherein in the step (2), bromoethyl thioglycolate and 3-aminopropyl trimethoxysilane are added according to the mass ratio of 1.4-1.7:1, and 20mL of 16% sodium bicarbonate solution is added to each gram of 3-aminopropyl trimethoxysilane.
5. The corrosion-resistant treatment process for corrosion-resistant alloy pipes according to claim 1, wherein in the step (3), silylated ethyl thioglycolate and o-allylphenol are added in a mass ratio of 1:1.08-1.13, and 43-44g of paraformaldehyde is added per mol of silylated ethyl thioglycolate.
6. The corrosion-resistant treatment process for the corrosion-resistant alloy pipe according to claim 1, wherein in the step (4), the mass ratio of the mercapto-silylated monomer to the triallylamine is 10:1.2-1.3, the addition amount of ethyl acetate is 1.1-1.3 times of the total mass of the mercapto-silylated monomer and the triallylamine, the addition amount of the initiator is 0.2-0.4% of the total mass of the mercapto-silylated monomer and the triallylamine, the addition amount of the epichlorohydrin is 18-19% of the mass sum of the mercapto-silylated monomer and the triallylamine, and the addition amount of sodium hydroxide is 3.4-3.6% of the mass sum of the mercapto-silylated monomer and the triallylamine.
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